Spectrally sensitized electrophotographic materials and processes

ABSTRACT

ORGANIC PHOTOCONDUCTORS ARE SPECTRALLY SENSITIZED WITH MEROCYANINE DYES WHICH CONTAIN A COMPLEX FUSED PYRIMIDINE-DIONE NUCLEUS LINKAGE BY A DOUBLE BOND OR A DIMETHINE LINKAGE TO A DESENSITIZING NUCLEUS.

United States Patent 3,565,616 SPECTRALLY SENSITIZED ELECTROPHOTO- GRAPHIC MATERIALS AND PROCESSES Frank G. Webster and Donald W. Heseltine, Rochester,

N.Y., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Continuation-impart of abandoned application Ser. No. 720,359, Apr. 10, 1968. This application Oct. 30, 1968, Ser. No. 771,974

Int. Cl. G03g 5/06 US. Cl. 961.6 30 Claims ABSTRACT OF THE DISCLOSURE Organic photoconductors are spectrally sensitized with merocyanine dyes which contain a complex fused pyrimidine-dione nucleus linkage by a double bond or a dimethine linkage to a desensitizing nucleus.

This application is a continuation-in-part of our copending US. patent application Ser. No. 720,359, filed Apr. 10, 1968, and now abandoned.

This invention relates to electrophotography, and more particularly to materials and elements useful in the electrophotographic process.

Elements useful in the electrophotographic process commonly comprise an electrically conductive support bearing a stratum including a photoconductive insulating layer which has a resistivity substantially greater in the dark than in light actinic thereto. Such elements can be used in electrophotographic processes, for example, by first adapting the element in the dark to obtain a uniformly high resistivity in the photoconductive insulating layer, and electrostatically charging the element in the dark to obtain a relatively high potential which may be either negative or positive in polarity. The element can then be exposed to a light pattern which lowers the resistivity and thereby the charge density of the illuminated areas imagewise in proportion to the intensity of illumination incident upon each point of the illuminated areas. A latent electrostatic image is obtained. Visible images can be formed from the latent electrostatic image in any convenient manner, such as by dusting with a finely divided, fusible pigment the particles of which bear an electrostatic charge opposite that remaining on the surface of the photoconductive insulating layer. Thereafter, the pigment particles can be fused to the surface to provide a permanent image.

Various photoconductive substances have been employed in photographic elements and processes of the type described above. Typical inorganic photoconductive materials include selenium and zinc oxide. Such inorganic photoconductive materials have inherent disadvantages, such as an inability to be readily adapted to reflex copying systems, or to produce images on transparent supports except by indirect means. Organic photoconductors avoid such disadvantages, but generally have relatively poor sensitivity to visible radiation. It has been proposed to increase the spectral sensitivity of organic photoconductors with certain cyanine or merocyanine dyes, for example, such as listed in Table D hereinafter. The spectral sensitivity imparted by such dyes has been very weak. It therefore appears highly desirable to provide effective spectral sensitizers for organic photoconductors.

One object of this invention is to provide novel sensitized organic photoconductors.

Another object of this invention is to provide novel spectrally sensitized organic photoconductor materials.

Still another object of this invention is to provide novel compositions of matter comprising organic photoconductors and certain spectral sensitizers.

A further object of this invention is to provide novel compositions of matter comprising organic photoconductor, binder and certain spectral sensitizers for the organic photoconductor.

Still another object of this invention is to provide a novel electrophotographic material including a conductive support having coated thereon an insulating layer containing spectrally sensitized organic photoconductor.

A further object of this invention is to provide methods for spectrally sensitizing organic photoconductors.

Still other objects of this invention will be apparent from the following disclosure and the appended claims.

In accordance with one embodiment of this invention, novel compositions of matter are provided comprising organic photoconductors spectrally sensitized with the dyes defined more fully below. These compositions can be incorporated in a suitable binder and coated on a conductive support for use in electrophotography.

In another embodiment of this invention, compositions of matter are provided comprising organic photoconductors spectrally sensitized with the dyes described be low, dispersed in an insulating binder. These compositions of matter can be coated on a conductive support and used in electrophotographic processes.

In still another embodiment of this invention, electrophotographic materials are provided comprising a conductive support having coated thereon a layer comprising an insulating binder, an organic photoconductor and a spectral sensitizing quantity of a dye defined more fully below.

In another embodiment of this invention, a method is provided for spectrally sensitizing organic photoconductors which comprises mixing a dye of the type described below with an organic photoconductor, in a concentration sufiicient to efiectively spectrally sensitize the organic photoconductor. Preferably, the dye and organic photoconductor are mixed in a suitable solvent.

The spectral sensitizing dyes which are employed in this invention are certain merocyanine dyes containing certain complex fused pyrimidinedione nuclei which, when incorporated in a test negative gelatin silver bromoiodide emulsion consisting of 99.35 mole percent bromide and .65 mole percent iodide, at a concentration of 0.2 millimole of dye per mole of silver halide, desensitize the emulsion more than 0.4 log B when the test emulsion is coated on a support, exposed through a step wedge in a sensitometer (to obtain D to light having a wavelength of 365 nm., processed for three minutes at 20 C. in Kodak Developer Dl9, and is fixed, washed and dried. As used herein and in the appended claims the test negative silver bromoiodide emulsions are prepared as follows:

In a container with temperature control is put a solution with the following composition:

Potassium bromideg. Potassium iodide-5 g.

Gelatin65 g. Waterl700 c.c.

And in another container is put a filtered solution consisting of:

Silver nitrate200 g.

Water2000 c.c.

Solution A is kept at a temperature of 54 C. during precipitation and ripening, while solution B is put in a separating funnel at a temperature of 54 C. The silver nitrate solution runs from the separating funnel through a calibrated nozzle into the container, the contents of which are kept in constant motion during precipitation and ripening, and later during finishing, by a mechanical stirrer. The precipitation is conducted over a period of minutes.

The developer employed in the test referred to above is Kodak developer D-19 which has the following composition:

G. N-Methyl-p-aminophenol sulfate 2.0 Sodium sulfite, desiccated 90.0 Hydroquinone 8.0 Sodium carbonate, monohydrated 52.5 Potassium bromide 5.0

Water to make 1.0 liter.

, As indicated above, the merocyanine dyes employed in this invention desensitize conventional negative silver halide emulsions. Such emulsions are inherently sensitive to blue radiation. The present dyes reduce that sensitivity. In addition, these dyes fail to provide practical spectral sensitization for such emulsions. Therefore, it was quite unexpected to find that they spectrally sensitized organic photoconductors.

Another characteristic of the cyanine dyes of this invention is that they are substantially non-photoconductive. The term substantially non-photoconductive as used herein means that no image is formed when a solution of 0.002 g. of the dye and 0.5 g. of polyester binder (described in Examples 1 to 3 below) are dissolved in 5.0 ml. of methylene chloride, and is coated and tested (in the absence of any photoconductor) as described in Examples 1 to 3 below.

The merocyanine dyes of this invention increase the speed of organic photoconductors by extending or increasing the response of the photoconductor to visible radiation (i.e., radiation in the range of about 400 nm. to 700 nm.). In the concentrations used, the dyes herein appear to function as spectral sensitizers when employed with efiicient organic photoconductors. When the organic photoconductor used is poor or inefficient, the dyes seem to function as speed increasing compounds as well as spectral sensitizers.

The merocyanine dyes that are useful in practicing the invention include those comprising first and second 5- to fi-membered nitrogen containing heterocyclic nuclei joined by a linkage consisting of a double bond or a dimethine bridge; the first of said nuclei being a complex fused pyrimidinedione nucleus, joined through the 3-carbon atom thereof, to said linkage; and said second nucleus being an electron-accepting nucleus of the type used in cyanine dyes joined at a carbon atom thereof to the said linkage. The complex fused pyrimidinedione nuclei employed in the dyes of this invention feature a fused nucleus attached to the 1- and 2-at0ms of the pyrimidinedione nucleus. The fused nucleus can be a. cyclic nucleus, such as a heterocyclic ring.

The preferred merocyanine dyes that are useful herein include those represented by the following general formula:

wherein n and In each represents a positive integer of from 1 to 2; L represents a methine linkage, e.g., CH=, C(CH C(C H etc., R represents an alkyl group, including substituted alkyl (preferably a lower alkyl containing from 1 to 4 carbon atoms) e.g., methyl, ethyl, propyl, isoprgpyl, butyl, hexyl, cyclohexyl, decyl, dodecyl, etc., and substituted alkyl groups (preferably a substituted lower alkyl containing from 1 to 4 carbon atoms) such as hydroxyalkyl group, e.g., fl-hydroxyethyl, w=hydroxybutyl, etc., an. a koxy lkyl g o p, -g-, fi-mthoxyethyl, w-butoxybutyl, etc., a carboxyalkyl group e.g., p-carboxyethyl, w-carboxybutyl, etc., a sulfoalkyl group, e.g., fl-sulfoethyl, w-sulfobutyl, etc., a sulfatoalkyl group, e.g., fl-sulfatoethyl, w-sulfatobutyl, etc., and acyloxyalkyl group, e.g., ,B-acetoxyethyl, 'y-acetoxypropyl, w-butyryloxybutyl, etc., an alkoxycarbonylalkyl group, e.g., [i-methoxycarbonylethyl, w-ethoxycarbonylbutyl, etc., or an aralkyl group, e.g., benzyl, phenethyl, etc., and the like; an alkenyl group, e.g., allyl, l-propenyl, Z-butenyl, etc., or, any aryl group, e.g., phenyl tolyl, naphthyl, methoxyphenyl, chlorophenyl, etc.; Z represents the non-metallic atoms necessary to complete an electron-accepting heterocyclic nucleus selected from the group including a nitrobenzothiazole nucleus, e.g., S-nitrobenzothiazole, 6-nitrobenzothiazole, 5-chloro-6-nitrobenzothiazole, etc.; a nitrobenzoxazole nucleus, e.g., S-nitrobenzoxazole, 6-nitrobenzoxazole, 5-chloro-6-nitrobenzoxazole, etc.; a nitrobenzoselenazole nucleus, e.g., S-nitrobenzoselenazole, 6- nitrobenzoselenazole, S-chloro 6 nitrobenzoselenazole, etc.; an imidazo[4,5-b]quinoxaline nucleus, e.g., imidazo [4,5 -b] quinoxaline, 1,3-dialkylimidazo [4,5 -b] quinoxaline such as 1,3-diethylimidazo[4,5-b]quinoxaline, 6-chloro- 1,3-diethylimidazo [4,5-b]quin0xaline, etc., 1,3-dialkenylimidazo[4,5-b1quinoxaline such as 1,3-diallylimidazo- [4,5-b]quinoxaline, 6-chloro 1,3 diallylimidazo[4,5-b] quinoxaline, etc., 1,3-diarylimidazo[4,5-b]quin0xaline such as 1,3-diphenylimidazo[4,5-b]quinoxaline, fi-chloro- 1,3-dipheny1imidazo[4,5-b1quinoxaline, etc.; a 3,3-dialkyl- 3H-pyrrol0[2,3-b]pyridine nucleus, e.g., 3,3-dimethyl- 3 H-pyrrolo [2,3-b] pyridine, 3 ,3diethyl-3 H-pyrrolo [2,3 -b] pyridine, etc.; a 3,3-dialkyl-nitro-3H-indole, e.g., 3,3-dimethyl 5 nitro-3H-indole, 3,3-diethyl-5-nitro-3H-indole, 3,3-dimethyl-6-nitro-3H-indole, etc.; a thiazolo[4,5- bJquinoline nucleus; or a nitroquinoline, e.g., S-nitroquinoline, 6-nitroquinoline, etc.; and Q represents the nonmetallic atoms required to complete a fused heterocyclic ring containing from 5 to 6 atoms in said ring, which ring may contain a second hetero atom such as oxygen, sulfur, selenium, or nitrogen, such as the following nuclei: 8. thiazole nucleus, e.g., thiazole 4-methylthiazole, 4-phenylthiazole, S-methylthiazole, S-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4 (2 thienyl)thiaz0le, benzothiazole, 4-chlorobenzothiazole, S-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4- methylbenzothiazole, S-methylbenzothiazole, 6-methylbenzothiazole, S-bromobenzothiazole, 6-bromobenzothiazole, 6-phenylbenzothiazole, S-phenylbenzothiazole, 4- methoxybenzothiazole, S-methoxybenzothiazole, 6-methoxybenzothiazole, 5-iodobenzothiazole, 6 iodobenzothiazole, 4-ethoxybenzothiazole, 5 ethoxybenzothiazole, tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole, 5,- 6-dioxymethylenebenzothiazole, 5 hydroxybenzothiazole, 6-hydroxybenzothiazole, a-naphthothiazole, fl-naphthothiazole, S-methoxy [3,5 naphthothiazole, 5 ethoxy-B- naphthothiazole, 8-methoxy-anaphthothiazole, 7 methoxy-a-naphthothiazole, 4'-methoxythianaphtheno-7,6,- 4,5-thiazole, etc.; an oxazole ring, e.g., 4-methyloxazole, S-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyl0xazole, 4,5-dimethyloxazole, 5-phenyloxazole, benzoxazole, 5-chlorobenzoxazole, S-methylbenzoxazole, S-phenylbenzoxazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, S-methoxybenzoxyazole, S-ethoxybenzoxazole, 5-chloronaphthoxazole, 6-methoxybenzoxazole, S-hydroxybenzoxazole, 6-hydroX- ybenzoxazole, a-naphthoxazole, p-naphthoxazole, etc.; a selenazole ring, e.g., 4-methylselenazole, 4-phenylselenazole, benzoselenazole, S-chlorobenzoselenazole, S-methoxybenzoselenazole, 5-hydroxybenzoselenazole, tetrahydrobenzoselenazole, a-naphthoselenazole, fl-naphthoselenazole, etc.; a thiazoline ring, e.g., thiazoline, 4-methylthiazoline, etc.; a pyridine ring, e.g., pyridine, 3-methylpyridine, 4-methylpyridine, etc.; a quinoline ring, e.g., quinoline, 3-methylquinoline, S-ethylquinoline, 6-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline, etc.; a 3,. -dialkylindolenine ring, e.g', 3,3-dimethylindolenine,

3,3-diethylindolenine, etc., an imidazo ring, e.g., imida- Zole, l-alkylimidazole, l-alkyl 4,5 dimethylimidazole, benzimidazole, l-alkylbenzimidazole, 1-aryl-5,6-dichlorobenzimidazole, l-alkylnaphthimidazole, l-aryl-B-naphthimidazole, 1-alkyl-S-methoxy-a-naphthimidazole, etc., and the like. Other electron-accepting nuclei defined by Z in above Formula I that are useful include nitrothiazole, nitronaphthothiazole, nitrooxazole, nitronaphthoxazole, nitroselenazole, nitronaphthoselenazole, and nitropyridine nuclei. Dyes of Formula I wherein Q represents the atoms required to complete a fused pyridine nucleus are especially useful and are the preferred dye species of the invention.

As used herein and in the appended claims, electronaccepting nucleus refers to those nuclei which, when converted to a symmetrical carbocyanine dye and added to gelatin silver chlorobromide emulsion containing 40 mole percent chloride and 60 mole percent bromide, at a concentration of from 0.01 to 0.2 gram dye per mole of silver, cause by electron trapping at least about an 80 percent loss in the blue speed of the emulsion when sensitometrically exposed and developed three min. in Kodak developer D-19 at 20 C., the composition of which is given above. Preferably, the electron-accepting nuclei are those which, when converted to a symmetrical carbocyanine dye and tested as just described above, essentially completely desensitize the test emulsion to blue radiation. Substantially complete desentization as used herein, results in at least a 90 percent, and preferably a 95 percent loss of speed to blue radiation.

The cyanine dyes defined by Formula I above are conveniently prepared, for example, by heating a mixture of (l) a heterocyclic compound of the formula:

Whemin 1, X and Z are as previously defined, and R represents methyl, ethyl, benzyl, etc., and (2) a complex fused pyrimidinedione compound of the formula:

(III) $1) NC amounts of (1) a compound of the formula:

(IV) H"; ,0 CH

and (2) ethylisoformanilide, without a solvent or in an inert solvent medium such as m-cresol, l-methyl pyrrolidinone, etc., followed by separation and recrystallization from appropriate solvents, e.g., pyridine. Further details for the preparation of the dyes and intermediates herein can be had by reference to our copending application; Ser. No. 639,024, filed May 17, 1967, wherein such dyes and their preparations are described.

Included among the dyes of Formula I above are the following typical dye compounds listed in Table A below The general method of their preparations is illustrated with Dye No. I.

TABLE A Compound Dye N0.:

(I) 3-[(1,3-diethyL2(1II)-in1idaze[4,5-b]quinoxalinylidene) elthyhdene]-2H-pyrnnido[2,l-albeuzothiazole-2,4(3H)- The above dye was prepared by heating a mixture of 0.8 g. (1 mol+50% excess) of S-anilinomethylene-ZH- pyrimido[2,1-b]benzothiaZole-2,4-(3H)-dione, 0.7 g. (1 mol) of 1,3-diethyl-2-methylimidazo-[4,5-b] quinoxalinum p-toluenesulfonate and 0.2 g. (1 mol+50% excess) of triethylarnine in 20 ml. of acetic anhydride at reflux temperature for 15 minutes. The reaction mixture is concentrated to dryness using a rotary evaporator. The residue is stirred in methanol, filtered and the solid is dissolved in hot pyridine, the solution is filtered and methanol is added. After chilling the solution, the resulting crystals are collected on a filter, and washed with methanol. The crude dye is dissolved in chloroform and passed through a neutral alumina column (activity II). The dye is isolated by concentrating the chloroform solution using a rotary evaporator. The yield of red crystals is 16% and they have a melting point greater than 310 C.

Compound Dyes such as illustrated above can be used alone, or a combination of one or more of the above described dyes can be used to impart the desired spectral sensitivity. All of them are spectral sensitizers for organic photoconductors. Suitable organic photoconductors which are effectively spectrally sensitized by such dyes include both monomeric and polymeric organic photoconductors. The invention is particularly useful in increasing the speed of organic photoconductors which are substantially insensitive, or which have low sensitivity (e.g., a speed less than 25 but generally less than 10 when tested as described in Examples 1 to 3) to radiation of 400 to 700 nm.

An especially useful class of organic photoconductors is referred to herein as organic amine photoconductors. Such organic photoconductors have as a common structural feature at least one amino group. Useful organic photoconductors which can be spectrally sensitized in accordance with this invention include, therefore, arylamine compounds comprising (1) diarylamines such as diphenylamine, dinaphthylamine, N,N'-diphenylbenzidine, N-phenyl-l-naphthylamine; N-phenyl 2 naphthylamine; N,N- diphenyl-p-phenylenediamine; 2 carboxy 5 chloro 4- methoxydiphenylamine; p-anilinophenol; N,N'-di-2-naphthyl-p-phenylene diamine; 4,4-benzylidene-bis(N,N-diethyl-m-toluidine) those described in Fox U.S. Pat. 3,240,- 597 issued Mar. 15, 1966, and the like, and (2) triarylamines including (a) non-polymeric triarylamines, such as triphenylamine, N,N,N',N-tetraphenyl m phenylenediamine; 4-acetyltriphenylamine, 4 hexanoyltriphenylamine, 4-lauroyltriphenylamine; 4-hexyltriphenylamine, 4- dodecyltriphenylamine, 4,4'-bis(diphenylamino) benzil, 4,4'-bis(diphenylamino)-benzophenone, and the like, and (b) polymeric triarylamines such as p0ly[N,4-(N,N',N- triphenyl'benzidine)]; polyadipyltriphenylamine, polysebacyltriphenylamine; polydecamethylenetriphenylamine; poly N (4 vinylphenyl) diphenylamine, poly N- (vinylphenyl)-a,a'-dinaphthylamine and the like. Other useful amine-type photoconductors are disclosed in U.S. Pat. 3,180,730, issued Apr. 27, 1965.

Other very useful photoconductive substances capable of being spectrally sensitized in accordance with this invention are disclosed in Fox U.S. Pat. 3,265,496 issued Aug. 9, 1966, and include those represented by the following general formula:

wherein A represents a mononuclear or polynuclear divalent aromatic radical, either fused or linear (e.g. phenylene, naphthalene, biphenylene, binaphthalene, etc.) or a substituted divalent aromatic radical of these types wherein said substituent can comprise a member such as an acyl group having from 1 to about 6 carbon atoms (e.g., acetyl, propionyl, butyryl, etc.), an alkyl group having from 1 to about 6 carbon atoms (e.g., methyl, ethyl, propyl, butyl, etc.), an alkoxy group having from 1 to about 6 carbon atoms (e.g., methoxy, ethoxy, propoxy, pentoxy, etc.) or a nitro group; A represents a mononuclear or polynuclear monovalent aromatic radical, either fused or linear (e.g., phenyl, naphthyl, biphenyl, etc.); or a substituted monovalent aromatic radical wherein said substituent can comprise a member, such as an acyl group having from 1 to about 6 carbon atoms (e.g., acetyl, propionyl, butyryl, etc.), an alkyl group having from 1 to about 6 carbon atoms (e.g., methyl, ethyl, propyl, butyl, etc.), an alkoxy group having from 1 to about 6 carbon atoms (e.g., methoxy, propoxy, pentoxy, etc.), or a nitro group; Q can represent a hydrogen atom, a halogen atom or an aromatic amino group, such as ANH-; b represents an integer from 1 to about 12, and G represents a hydrogen atom, a mononuclear or polynuclear aromatic radical, either fused or linear (e.g., phenyl, naphthyl, biphenyl, etc.), a substituted aromatic radical wherein said substituent comprises an alkyl group, an alkoxy group, an acyl group, or a nitro group, or a poly(4-vinylphenyl) group which is bonded to the nitrogen atom by a carbon atom of the phenyl group. Certain nitrogen heterocyclic compounds are also useful photoconductors in the invention such as, for example, l,3,5-triphenyl-2-pyrazo1ine, 2,3,4,5 tetraphenylpyrrole, etc.

Polyarylalkane photoconductors are particularly useful in producing the present invention. Such photoconductors are described in U.S. Pat. 3,274,000; French Pat. 1,383,461 and in a copending application of Seus et al. Ser. No. 624,233, Photoconductive Elements Containing Organic Photoconductors filed Mar. 20, 1967, and now abandoned. These photoconductors include leucobases 0f diaryl or triaryl methane dye salts, 1,1,1-triarylalkanes wherein the alkane moiety has at least two carbon atoms and tetraarylmethanes, there being substituted an amine group on at least one of the aryl groups attached to the alkane and methane moieties of the latter two classes of photoconductors which are non-leuco base materials.

Preferred polyaryl alkane photoconductors can be represented by the formula:

wherein each of D, E and G is an aryl group and J is a hydrogen atom, an alkyl group, or an aryl group, at least one of D, E and G containing an amino substituent. The aryl groups attached to the central carbon atom are preferably phenyl groups, although naphthyl groups can also be used. Such aryl groups can contain such substituents as alkyl and alkoxy typically having 1 to 8 carbon atoms, hydroxy, halogen etc. in the ortho, meta or para positions, ortho-substituted phenyl being preferred. The aryl groups can also be joined together or cyclized to form a fluorene moiety, for example. The amino substituent can be represented by the formula wherein each R can be an alkyl group typically having 1 to 8 carbon atoms, a hydrogen atom, an aryl group, or together the necessary atoms to form a heterocyclic amino group typically having 5 to 6 atoms in the ring such as morpholino, pyridyl, pyrryl, etc. At least one of D, E, and G is preferably p-dialkylaminophenyl group. When I is an alkyl group, such an alkyl group more generally has 1 to 7 carbon atoms.

Representative useful polyarylalkane photoconductors include the compounds listed below:

methane. (12). 4,4-bis(diethylamino)-2,2-diethoxytriphenylmethane. (l3) 4,4-bis (dimethylamino)-1,1,1-triphenylethane. (14) 1-(4-N,Ndimethy1arninophenyl)-l,1-diphenylethane. (15) 4dimethylarninotetraphenylmethane. (16) 4-diethylaminotetraphenylmethane.

As described herein a wide variety of photoconductor compounds can be spectrally sensitized with the dyes referred to above. Some organic photoconductors will, of course, be preferred to others; but in general useful results may be obtained from substantially all of the presently known organic photoconductors.

The following Table C comprises a partial listing of U.S. patents describing such organic photoconductors and compositions which can be used in place of those more particularly described herein,

TABLE Patent Inventor numbers Schleslnge Cassiers Apr. 28, 1964" .Tune 30, 1964..-. do July 14, 1964..-. July 21,1964

Jul 21,19e4- June 5,1962..."

Klupfel et al Neugebauer et a1 Cassiers et a1 Schlesingen Kosehe et al Aug. 9 1966 3,265 497 Noe et a1 Sept. 20, 1966 3,

The spectrally sensitized organic photoconductor compositions of this invention can, in certain arrangements, be employed in electrophotographic elements in the absence of binder. For example, the photoconductor itself s sometimes capable of film formation, and therefore requires no separate binder. An example of such film-forming photoconductor is poly(vinylcarbazole). However, the more common arrangement is to provide a binder for the spectrally sensitized organic photoconductive materials. Any suitable binder material can be utilized for the spectrally sensitized organic photoconductors of the invention. Such binders should possess high dielectric strength, and have good insulating properties (at least in the absence of actinic radiation) as well as good film forming properties. Preferred binder materials are polymers such as polystyrene, poly(methylstyrene), styrenebutadiene polymers, poly(vinyl chloride), poly (vinylidene chloride), poly(viny1 acetate), vinyl acetate-vinyl chloride polymers, poly(vinyl acetals), polyacrylic and methacrylic acid esters, polyesters such as poly(ethylene alkaryloxyalkylene terephthalates), phenol-formaldehyde resins, polyamides, polycarbonates and the like.

The photoconductive compositions of the invention can be coated on any of the electrically conductive supports conventionally used in electrophotographics processes, such as metal plates or foils, metal foils laminated to paper or plastic films, electrically conductive papers and films, papers and films coated with transparent electrically conductive resins and the like. Other useful conducting layers include thin layers of nickel coated by high vacuum deposition and cuprous iodide layers as described in US. Pat. 3,245,833. Transparent, translucent or opaque support material can be used. Exposure by reflex requires that the support transmit light while no such requirement is necessary for exposures by projection. Similarly transparent supports are desired if the reproduction is to be used for projection purposes; translucent supports are preferred for reflex prints; and opaque supports are adequate if the image is subsequently transferred by any means to another support, the reproduction is satisfactory as obtained, or the reproduction is to be used as a printing plate for preparing multiple copies of the original.

The quantity of the above-described dye required to spectrally sensitize an organic photoconductor varies with the results desired, the particular dye used, and the particular organic photoconductor used. Best results are obtained with about .01 to 10 parts by weight dye and about 1 to 75 parts by weight of the organic photoconductor based on the photoconductive composition. Binder can be employed in such compositions, when desired, at preferred ranges of 25 to 9 parts by weight. In addition, the composition can contain other sensitizers, either spectral sensitizers .or speed increasing compounds, or both.

As used herein and in the appended claims, the terms insulating and electrically conductive have reference to materials the surface resistivities of which are greater than 10 ohms per square unit (e.g., per square foot) and less than 10 ohms per square unit (e.g., per square foot) respectively.

Coating thicknesses of the photoconductive compositions of the invention on a support can vary widely. As a general guide, a dry coating in the range from about 1 to 200 microns is useful for the invention. The preferred range of dry coating thickness is in the range from about 3 to 50 microns.

To produce a reproduction of an image utilizing the electrophotographic elements of our invention, the photoconductive layer is preferably dark adaptand then is charged either negatively or positively by means of, for example, a corona discharge device maintained at a potential of from 6000-7000 volts. The charged element is then exposed to light through a master, or by reflex in contact with a master, to obtain an electrostatic image corresponding to the master. This invisible image may then be rendered visible by being developed by contact with a developer including a carrier and toner. The carrier can be, for example, small glass or plastic balls, or iron powder. The toner can be, for example, a pigmented thermosplastic resin having a grain size of from about 1-100 which may be fused to render the image permanent. Alternatively, the developer may contain a pigment or pigmented resin suspended in an insulating liquid which optionally may contain a resin in solution. If the polarity of the charge on the toner particles is opposite to that of the electrostatic latent image on the photoconductive element, a reroduction corresponding to the original is obtained. If, however, the polarity of the toner charge is the same as that of the electrostatic latent image, a reversal or negative of the original is obtained.

Although the development techniques described hereinabove produce a visible image directly on the electrophotographic element, it is also possible to transfer either the electrostatic latent image, or the developed image to a second support which may then be processed to obtain the final print. All of these development techniques are well known in the art and have been described in a number of US. and foreign patents.

This invention is further illustrated by the following examples.

EXAMPLES 1 TO 3 These examples show the great increase in speed of organic photoconductors when the dyes employed in this invention are added thereto. This increase in speed is due to the spectral sensitivity imparted to the photoconductor by the dyes described herein. The examples also show that the maximum sensitivity peaks (abs maxi) occur in most cases at radiations in the region of the spectrum of from about 500 to 575 nm. The testing of the sensitizing properties of the dyes is carried by the following procedure.

A series of solutions are prepared consisting of 5.0 ml. methylene chloride (solvent); 0.15 g. 4,4'-bis(diethylamino) 2,2 dimethyltriphenylmethane (organic photoconductor); 0.50 g. polyester composed of terephthalic acid and a glycol mixture comprising a 9:1 weight ratio of 2,2 bis[4 (2 hydroxyethoxy)phenyl] propane and ethylene glycol (binder) and 0.0065 g. of the spectral sensitizing dye indicated by identifying number from above Table A. Each solution is coated on an aluminum surface maintained at 25 C., and dried. All operations are carried out in a darkened room. A sample of each coating is uniformly charged by means of a corona to a potential of about 600 volts and exposed through a transparent member bearing a pattern of varying optical density to a 3000 K. tungsten source. The resultant electrostatic image pattern is then rendered 'visible by cascading a developer composition comprising finely divided colored thermoplastic electrostatically responsive toner particles carried on glass beads over the surface of the element. The image is then developed by deposition of the toner in an imagewise manner on the element. (Other development techniques such as those described in US. 2,786,439; 2,786,440; 2,786,441; 2,811,465; 2,874,063; 2,984,163; 3,040,704; 3,117,884; Re. 25,779; 3,297,691; 2,551,582; and in RCA Review, vol. 15 (1954) pages 469484, can be used with similar results.) An image is formed on each sample, as indicated in Table I. Another sample of each coating is tested to determine its electrical speed and maximum sensitivity peak. This is accomplished by giving each element a positive or negative charge (as indicated in Table I) with a corona source until the surface potential, as measured by an electrometer probe, reaches 600 volts. It is then exposed to light from a 3000 K. tungsten source of 20-foot candle illuminance at the exposure surface. The exposure is made through a stepped density gray scale. The exposure causes reduction of the surface potential of the element under each step of the gray scale from its initial potential, v to some lower potential, V, whose exact value depends on the actual amount of exposure in meter-candle-seconds received by the area. The results of these measurements are plotted on a graph of surface potential V vs. log exposure for each step. The actual speed of each element is expressed in terms of the reciprocal of the exposure required to reduce the surface potential by 100 volts. Hence, the speeds given in Table I are the numerical expression of divided by the exposure in meter-candle-seconds required to reduce the 600 volts charged surface potential by 100 volts. The results are shown in Table I below.

TAB LE I Referring to the above Table I, it will be seen that the control example containing the same photoconductor but no dye shows speeds of only 8 and 7 for the positively and negatively charged surfaces, respectively, whereas the corresponding values for those of the invention represented by Examples 1 to 3 are clearly of a different order of magnitude. For example, the highest speed is shown by Example 3 (Dye No. VI) of 1090 and 915 for the positively and negatively charged surfaces, respectively, with maximum sensitivity peak at 550 nm., thus indicating a speed increase over that of the control by a factor of about 130 for both the positively charged and the negatively charged surfaces. Also of great significance is the extension of the absolute sensitivity to the region of 550 nm. Even with the least speed shown for the compositions and elements of the invention as illustrated by Example 1 (Dye No. III) the improvement in speed is impressive in comparison with that of the control by factors of about 80 and 60 for the positive charged and negatively charged surfaces, respectively. Similar results are obtained when dyes I, II, V, VI-IX or the dyes listed after Table A, are substituted for dyes III, IV or VI in Examples 13.

Similar results to those shown in above Table I are obtained, when, for example, the organic photoconductor 4,4 bis(diethylamino)-2,2'-dimethyltriphenylmethane is replaced with 0.15 g. of triphenylamine (using the p-toluenesulfonate salt of each dye), or 1,3,5-triphenyl-2-pyrazoline, or 2,3, 4,S-tetraphnylpyrrole, or 4,4-bis-diethylaminobenzophenone or when other dyes of the invention embraced by Formula I above are used. These results show that the dyes of this invention effectively spectrally sensitize a wide variety of organic photoconductors. The dyes of this invention are not in themselves photoconductive. Also, it should be noted that the above mentioned photoconductors when used alone have very low photoconductive speed to visible light. However, as shown by the tests, the combination of the dyes of the invention with the photoconductors of the invention provide compositions and elements of outstanding speed and excellent quality of image.

This invention is highly unexpected because dyes pre viously suggested for spectral sensitizers impart weak spectral sensitization to organic photoconductors. Typical dyes proposed by the prior art as spectral sensitizers, which produce weak spectral sensitization in these systems, are shown in Table D below.

thiaearboeyanine hydroxide. (G) 1-ethyl-3-methylthia-2-cyaninc chloride. (H) 1,1-diethyl-2,2-cyanine chloride.

As indicated previously, the dyes of this invention act as desensitizers for conventional negative type photographic silver halide emulsions.

The invention has been described in detail with particular reference to preferred embodiments thereof, but, it will be understood that variations and modifications can be effected within the spirit and scope of the invention described hereinabove and in the appended claims.

We claim:

1. A composition of matter comprising an organic photoconductor spectrally sensitized with a merocyanine dye comprising first and second 5- to 6-membered nitrogen containing heterocyclic nuclei joined together by a linkage selected from the group consisting of a double bond and a dimethine linkage; the first of said nuclei being a pyrimidinedione nucleus having attached to the 1- and 2-atoms thereof the non-metallic atoms required to complete a ring containing from 5 to 6 atoms, said first nucleus being joined at the 3-carbon atom thereof to said linkage; and, said second nucleus being an electron-accepting nucleus.

2. A composition as defined by claim 1 wherein said linkage in said dye is a dimethine linkage.

3. A composition as defined in claim 1 wherein said electron-accepting nucleus of said dye is substituted by a nitro group at a carbon atom thereof.

4. A composition as defined in claim 1 wherein said electron-accepting nucleus of said dye is an imidazo[4,5- b]quinoxaline nucleus.

5. A composition as defined by claim 1 wherein said organic photoconductor is selected from the group consisting of: a triphenylamine; a l,3,S-triaryl-Z-pyrazoline; a 4,4'-bis(dialkylamino)-2,2'-dialkyltriarylamine; a 2,3,4, S-tetraarylpyrrole; and a 4,4-bis-dialkylaminobenzophenone.

6. A composition of matter comprising an organic photoconductor and a merocyanine dye selected from those represented by the following general formula:

wherein n represents a positive integer of from 1 to 2; L represents a methine linkage, R represents a member selected from the group consisting of an alkyl group, an alkenyl group, and an aryl group; Z represents the nonmetallic atoms necessary to complete an electron-accepting nucleus containing 5 to 6 atoms; and, Q represents the non-metallic atoms required to complete a fused heterocyclic ring containing 5 to 6 atoms in said ring.

7. A composition as defined in claim 6 wherein said Z of said dye represents the non-metallic atoms necessary to complete said electron-accepting nucleus selected from the group consisting of a nitrobenzothiazole nucleus, a nitrobenzoxazole nucleus, a nitrobenzoselenazole nucleus and an imidazo[4,5-b]quinoxaline nucleus.

8. A composition as defined in "claim 6 wherein said Q of said dye represents the non-metallic atoms necessary to complete a fused heterocyclic ring selected from the group consisting of a thiazole ring, an oxazole ring, a selenazole ring, a thiazoline ring, a pyridine ring, a quinoline ring, a 3,3-dialkylindolenine ring, and an imidazole ring.

9. A composition as defined by claim 6 wherein said organic photoconductor has the following formula:

wherein each of D, E and G is an aryl group and J is selected from the group consisting of a hydrogen atom, an alkyl group and an aryl group, at least one of D, E and G containing an amino substituent selected from the group consisting of a secondary amino group and a tertiary amino group.

10. A composition as defined by claim 6 wherein said organic photoconductor is selected from the group consisting of: triphenylamine; 1,3,5-triphenyl-2-pyrazoline; 4,4 bis(diethylamino) 2,2 dimethyltriphenylamine; 2,3,4,5-tetraphenylpyrrole; and, 4,4'-bis-diethylaminobenzophenone.

11. A composition as defined by claim 6 wherein said photoconductor comprises from 1 to 75 parts by weight of said composition, said photoconductor being spectrally sensitized with from .01 to parts by weight of said composition of said merocyanine dye.

12. A composition as defined by claim 6 wherein said organic photoconductor and said dye are incorporated in an insulating binder.

13. A composition as defined by claim 6 wherein Sm organic photoconductor and said dye are dispersed in from 25 to 99 parts by weight of a polyester of terephthalic acid and a glycol mixture consisting of a 9:1 weight ratio of 2,2'-bis[4-(2-hydroxyethoxy)phenyl]propane and ethylene glycol as insulating binder.

r; 14. A composition of matter comprising from 1 to 75 parts by weight of an organic photoconductor selected from the group consisting of: triphenylamine; 1,3,5-triphenyl 2 pyrazoline; 4,4 bis diethylamino-2,2-dir'nethyltriphenyhnethane; 2,3,4,5 tetraphenylpyrrole; 4,4- bis-diethylaminobenzophenone; said organic photoconductor being spectrally sensitized with from .01 to 10 14 dichloro 1,3 diphenyl 2(1H)-imidazo[4,5-b]quinoxalinylidene)ethylidene] 2H pyrido[1,2-a]pyrimidine- 2,4(3H)-dione.

15. A composition of matter as defined in claim 14 wherein said organic photoconductor and said dye are dispersed in from 25 to 99 parts by weight of a polyester of terephthalic acid and a glycol mixture consisting of a 9:1 weight ratio of 2,2-bis- [4-(Z-hydroxyethoxy)-phenyl]- propane and ethylene glycol as insulating binder.

16. An electrophotographic element comprising a conductive support having thereon a layer comprising an organic photoconductor in an insulating binder, said organic photoconductor being spectrally sensitized with a merocyanine dye comprising first and second 5- to 6-membered nitrogen containing heterocyclic nuclei joined together by a linkage selected from the group consisting of a double bond and a dimethine linkage; said first nucleus being a pyrimidinedione nucleus having attached to the land 2-atoms thereof the non-metallic atoms required to complete a ring containing from 5 to 6 atoms, said first nucleus being joined at the 3-carbon atom thereof to said linkage; and, said second nucleus being an electron-accepting nucleus.

17. An electrophotographic element as defined in claim 16 wherein said linkage in said dye is a dimethine linkage.

18. An electrophotographic element as defined in claim 16 wherein said electron-accepting nucleus of the said dye is substituted by a nitro group at a carbon atom thereof.

19. An electrophotographic element as defined in claim 16 wherein said electron-accepting nucleus of said dye is an imidaZo[4,5-b]quinoxaline nucleus.

20. An electrophotographic element as defined in claim 16 wherein said organic photoconductor is selected from the group consisting of: a triphenylamine; a 1,3,5-triaryl- Z-pyrazoline; a 4,4 bis(dialkylamino) 2,2'-dialkyltriaarylamine; a 2,3,4,5-tetraarylpyrrole; and a 4,4-bis-dialkylarninobenzophenone.

21. An electrophotographic element comprising a conductive support having thereon a layer comprising an organic photoconductor spectrally sensitized with a merocyanine dye selected from those represented by the following general formula:

wherein n represents a positive integer of from 1 to 2; L represents a methine linkage, R represents a member selected from the group consisting of an alkyl group, an alkenyl group and an aryl group; Z represents the nonmetallic atoms necessary to complete an electron-accepting nucleus containing 5 to 6 atoms; and, Q represents the non-metallic atoms required to complete a fused heterocylic ring containing 5 to 6 atoms 1n said ring.

22. An electrophotographic element as defined in claim 21 wherein said Z of said dye represents the non-metallic atoms necessary to complete said electron-accepting nucleus selected from the group consisting of a nitrobenzothiazo le nucleus, a nitrobenzoxazole nucleus, a nitrobenzoselenazole nucleus and an imidazo[4,5-b]quinoxaline nulceus.

23. An electrophotographic element as defined in claim 21 wherein said Q of said dye represents the non-metallic atoms necessary to complete a fused herterocyclic ring selected from the group consisting of a thiazole ring, an oxazole ring, a selenazole ring, a thiazoline ring, a pyridine ring, a quinoline ring, a 3,3-dialkylindolenine ring, and an imidazole ring.

24. An electrophotographic element as defined in claim 21 wherein said organic photoconductor has the following formula:

wherein each of D, E and G is an aryl group and J is selected from the group consisting of a hydrogen atom, an alkyl group and an aryl group, at least one of D, E and G containing an amino substituent selected from the group consisting of a secondary amino group and a tertiary amino group. i

25. An electrophotographic element as defined in claim 21 wherein said organic photoconductor is selected from the group consisting of: triphenylamine; 1,3,5-triphenyl-2- pyrazoline; 4,4'-bis-(diethylamino) 2,2 dimethyltriphenylalmine; 2,3,4,5-tetraphenylpyrrole; and 4,4'-bis-diethylaminobenzophenone.

26. An electrophotographic element as defined in claim 21 wherein said organic photoconductor comprises from 1 to 75 parts by weight of said composition, said photoconductor being spectrally sensitized with from .01 to 10 parts by weight of said composition of said merocyanine dye.

27. An electrophotograp'hic element as defined in claim 21 wherein said organic photoconductor and said dye are incorporated in an insulating binder.

28. An electrophotographic element as defined in claim 21 wherein said organic photoconductor and said dye are dispersed in from 25 to 99 parts by Weight of a polyester of terephthalic acid and a glycol mixture consisting of a 9: 1 weight ratio of 2,2'-bis-[4-(2 hydroxyethoxy)-phenyl]- propane and ethylene glycol as insulating binder.

29. An electrophotographic element comprising a conductive support having thereon a layer comprising from 1 to parts by weight of an organic photoconductor selected from the group consisting of: triphenylamine; 1,3,5 triphenyl-Z-pyrazoline; 4,4'-bis-diefihylamino-2,2'- dimetehyltriphenylmethane; 2,3,4,5 tetraphenylpyrrole; 4,4'-bis-diethy1aminobenzophenone; said organic photoconductor being spectrally sensitized with from .01 to 10 parts by weight of a dye selected from the group consisting of 3-[(1,3-dietihyl 2(1H) imidazo[4,5-b]quinoxalinylidene)-ethylidene] 2H pyrido[1,2-a]pyrirnidine- 2,4(3H) dione; 3-[(6-ch1oro 1,3 dipheny1-2(1H)- imidazo[4,5 b]quinoxalinylidene) ethylidene] 2H- pyrido[1,2-a]-pyrimidine 2,4(3H) dione and 3-[(6,7- dichloro-1,3-diphenyl 2(1H) imidazo[4,5-b]quin'oxalinylidene)ethylidene] 2H pyrido[1,2-a]pyrimidine- 2,4(3H)-dione.

30. An electrophotographic element as defined in claim 29 wherein said organic photoconductor and said dye are dispersed in from 25 to 99 parts by weight of a polyester of terephthalic acid and a glycol mixture consisting of a 9:1 weight ratio of 2,2-bis-[4-(2-hydroxyethoxy)-phenyl]- propane and ethylene glycol as insulating binder.

References Cited UNITED STATES PATENTS CHARLES E. VAN HORN, Primary Examiner US. Cl. X.R. 

